DE2165803A1 - Detergents contg sulphonated phenol-formaldehyde resins - as greying inhibitors - Google Patents

Abstract

Detergents with improved soil-redeposition props. contain (a) >=1 surfactant; (b) >=1 builder salt selected from polymeric phosphates, sequestering agents and washing alkalies; and (c) 0.1-10 wt.% of >=1 water-soluble polycondensate of mol. wt. 500-1500, derived from the condensation product of 1 mole HCHO with 1.6-2 moles of a phenol, naphthol and/or (1-4C alkyl) phenol and contg. 1-2 SO3M gps. (where M is alkali metal or NH4, pref. Na) to each 2 aromatic gps. The detergents can be used to wash cellulose materials, synthetic fibre materials, chemically modified cellulose and treated cotton, as well as mixed fabrics. For washing cellulose materials, the detergents pref. also contain =5 (esp. 0.2-3) wt.% of CMC.

Description

Detergent containing anti-graying additives Es it is known that detergents and cleaning agents that contain surface-active compounds Adding substances that improve the dirt-carrying capacity of the washing liquors.

Such substances, referred to below as graying inhibitors prevent the detached dirt from being resorbed on the cleaned surfaces. These are mostly polymers that are either made from natural substances such as cellulose, Gelatin or glue or by polymerizing vinyl compounds such as acrylic acid, Methacrylic acid, maleic acid, vinyl acetate and vinyl pyrrolidone can be produced. Also the polysulfonates of vinyl polymers as well as polyesters and polyamides with one The content of carboxyl groups capable of salt formation has already been identified as graying-inhibiting Additives to detergents and cleaning agents recommended. From the connections in question However, only carboxymethyl cellulose has achieved greater technical importance, especially since they are all synthetic in their anti-graying effect Polymers. The carboxymethyl cellulose and the majority of the above However, synthetic polymers have the disadvantage that their anti-graying Effect on cellulose fibers is limited while they are washing synthetic Fiber material, chemically modified cellulose or refined cotton to a large extent are ineffective.

This disadvantage is particularly evident in relation to white textiles Made of polyester or polyolefin fibers, non-iron cotton and blended fabrics from the mentioned Synthetic fibers with cellulose fibers noticeable, which turn gray during use despite frequent washing and thus become unsightly can. The aforementioned polyesters and polyamides lead to an essential one However, unlike vinyl polymers, they can be improved by strongly alkaline Detergent salts are partially saponified.

The task was to develop a means that the above Does not have disadvantages.

The invention relates to detergents with a content of at least a surface-active washing active substance and at least one building salt the class of polymer phosphates, sequestering agents and washing alkalis as well as at least containing a water-soluble alkali metal or ammonium salt of sulfonic acid groups Polycondensates, characterized in that the amounts of 0.1 to 10 wt .-% present and a molecular weight of 500 to 1500 having salts of the polycondensates differs from a reaction product of one mole of formaldehyde and 1.6 to 2 moles of one Compound from the class of phenols, naphthols and 1 to 4 carbon atoms in derive the alkylphenols having alkyl groups and, in each case 2 aromatic Groups based, contain 1 to 2 sulfonic acid groups.

The salts of the polycondensates are known compounds, aie Reaction of phenol, o-cresol, m-cresol, p-cresol, isomeric alkylphenols with 2 to 4 carbon atoms in the alkyl chain, OC-naphthol or ß-naphthol and their mixtures with formaldehyde at temperatures above 500, for example 80 to 150 ° C, in the presence aqueous alkalis or nineral acids are available.

The sulfonation can be carried out using sulfuric acid monohydrate, oleum, chlorosulfonic acid or sulfur trioxide can be made. One can also use sulfonated phenols, Alkyl phenols and naphthols go out and this with formaldehyde condense. The polymeric sulfonic acids obtained are treated with alkalis, ammonia or organic ammonium bases, for example mono-, di- or triethanolamine, are neutralized. The sodium salts or sulfonated condensation products are preferably used Use.

In addition to the aforementioned condensates, the detergents contain customary ones Surface-active washing active substances, such as anionic, nonionic and zwitterionic Detergents, and also non-surface-active builder salts, for example condensed Phosphates, sequestrants and washing alkalis as well as gSf. others in detergent formulations Usual auxiliaries and additives.

Suitable washing raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, furthermore Olefin sulfonates, such as those obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide @ and then alkaline or acid hydrolysis, as well as alkyl sulfonates, such as those obtained from n-allcans by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or are obtainable by addition of isulphite to olefins. Also suitable are α-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.

Further compounds of this class which may be present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. Further sulfates come from ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isethionates.

Other suitable anionic detergent raw materials are alkali soaps from Fatty acids of natural or synthetic origin, e.g. the sodium soaps from Coconut, palm kernel or tallow fatty acids. Come as zwitterionic washing raw materials Alkylbetaines and in particular alkylsulfobetaines in question, for example 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

The anionic detergent raw materials can be in the form of sodium, potassium and arimonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present. If the anionic and zwitterionic compounds mentioned have a have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In compounds with an araliphatic The preferably unbranched alkyl chains contain hydrocarbon radicals on average 6 to 16 carbon atoms.

As non-ionic, surface-active washing active substances come in primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to O glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical contain. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms. By adding 3 to 15 moles of propylene oxide to the latter polyethylene glycol ethers or by converting them into the acetals, detergents are obtained which are able to withstand the are characterized by a particularly low foaming power.

Other suitable non-ionic washing raw materials are the water-soluble, 20 Üis containing 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Polyethylene oxide adducts with polypropylene glycol, ethylene diamine polypropylene glycol and Alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.

The compounds mentioned usually contain per propylene glycol unit 1 to 5 ethylene glycol units.

Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated can be used.

The building salts include the tripolyphosphates, especially that Pentasodium triphosphate. The triphosphates can also be condensed in a mixture with higher Phosphates, such as tetraphosphates, or their hydrolysis products, such as acidic or neutral pyrophosphates.

The condensed phosphates can also be wholly or partially through organic, complexing aminopolycarboxylic acids be replaced. Which includes especially alkali salts of nitrilotriacetic acid and lithylenediamine-vraacetic acid. The salts of diethylenetriaminopentaacetic acid and the higher salts are also suitable Homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reaction of polyamines with a molecular weight of 500 to 10,000 with chloroacetic acid or bromosetic acid Salts are produced in an alkaline medium. Further suitable aminopolycarboxylic acids are Poly- (N-succinic acid) -ethyleneimines and poly- (N-tricarballyic acid) -ethyleneimines with an average molecular weight of 500 to 500,000, which are analogous to the N-acetic acid derivatives are available.

Furthermore, complexing polyphosphonic acid salts can be present be, e.g. the alkali salts of aminopolyphosphonic acids, especially aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylene phosphonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used.

Alkali silicates, for example, can be used as washing alkalis, in particular Sodium silicate in which the ratio of Na20: SiO2 is 1: 3.5 to 1: 1. Other suitable washing alkalis are carbonates, bicarbonates and borates of sodium or potassium. The amount of alkaline reacting substances including alkali silicates and phosphates should be dimensioned so that the pil value of a usable lye ff for coarse items is 9 to 12 for delicates items 6 to 9.

Oxygen-releasing bleaches are another component of the mixture, such as alkali perborates, percarbonates, perpyrophosphates and persilicates as well as arnstoffperhydrat in question. Sodium perborate tetrahydrate is preferably used.

In order to stabilize the per compounds, the agents can contain magnesium silicate contain, for example in amounts of 3 to 20 wt .-%, based on the amount of Perborate. Agents to be used for washing textiles at temperatures below 700C, so-called cold washing agents can contain bleach activators from the class of N- and O-acyl compounds, especially tetraacetylethylenediamine or tetraacetylglycoluril, contained as a powder component. The ones from the bleach activator or from the per compound existing powder particles can be coated with coating substances such as water-soluble polymers, Fatty acids or granulated salts, such as alkali silicates, sodium sulfate or Disodium hydrogen phosphate, coated to cause an interaction between the per compound and the activator during storage.

The detergents can also contain optical brighteners, in particular Derivatives of diaminostilbene disulfonic acid or

their alkali metal salts of the formula: in which X and Y have the following meanings: NH2, NH-CH3, NH-CH2-CH2OH, CH3-N-CH2-CH2OH, N (CH2-CH2OH) 2, morpholino, dimethylmorpholino, NH-C6H5, NH-C6H4- SO3H, OCH3, Cl, where X and Y can be the same or different. Those compounds in which X is an anilino and Y is a diethanolamino or morpholino group are particularly suitable.

Optical brighteners of the diarylpyrazoline type with the following formula are also suitable: In this formula, Ar and Ar 'denote aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxy, sulphonic acid and sulphonamide groups or halogen atoms. A 1,3-diarylpyrazoline derivative is preferably used in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar is a p-chlorophenyl group. Further suitable whiteners are those of the naphthotriazole tllbenesulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarine and cyanoanthracene type.

Mixtures of optical healers can also be used.

The agents can also include enzymes from the class of the proteases, lipases and amylases or mixtures thereof.

Bacterial strains or felts, such as Bacillus, are particularly suitable subtilis and Streptoyces griseus used the enzymatic agents obtained Relatively resistant to alkali, per-compounds and anionic washing active substances are and are not yet significantly inactivated even at temperatures 500 and 700.

Further components contained in the agents according to the invention are neutral salts, especially sodium sulfate, bacteriostatic substances, such as halogenated phenolic ethers and thioethers, halogenated carbanilides and salicylanilides as well as halogenated diphenylmethanes, as well as dyes and fragrances.

Liquid agents can also contain hydrotropes and solvents contain, such as alkali salts of benzene, toluene or xylene sulfonic acid, urea, Glycerine, polyglycerine, di- or triglycol, polyethylene glycol, ethanol, i-propanol and ethereal alcohols.

If necessary, the detergents can also be known foam steaming agents contain, such as saturated fatty acids or their alkali metal soaps with 20 to 24 Carbon atoms, higher molecular weight fatty acid esters or triglycerides or trialkylmelamines.

To further increase the dirt-carrying capacity, additional known graying inhibitors, especially sodium cellulose glycolate (carboxymethyl cellulose) can be added. The joint use of the copolymers of the invention and of cellulose glycolate is particularly useful when cleaning textiles made from cellulose fibers and blended fabrics containing synthetic fibers are advantageous.

The qualitative and quantitative composition of the detergent depends largely depends on their area of application. The content of those to be used according to the invention Graying inhibitor is 0.1 to 10 in the composite detergents, preferably 0.2 to 5 percent by weight. The difference from 90 to 99.9, preferably 95 to 99.8 percent by weight is allotted to other detergent ingredients, their quantitative composition can correspond to the following scheme (data in percent by weight): 1 up to 40% of at least one compound from the class of the anionic, nonionic and zwitterionic washing active substances, 10 to 80% of at least one non-surface-active, Cleansing enhancing or complexing building salt, 10 to 50% of a Per-compound in particular sodium perborate containing water of crystallization or anhydrous, and their mixtures with stabilizers and activators, 0.1 to 20, o 'others Auxiliaries and additives.

The washing active substances can be up to 100, preferably 5 to 70% of compounds of the sulfonate and / or sulfate type, up to 100%, preferably 5 to 40% of nonionic compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50% consist of soap. The building salts can contain up to 100 %, preferably 25 to 95% of alkali metal triphosphates and their mixtures with Al- potassium metal pyrophosphates, up to 100%, preferably 5 to 50%, of an alkali metal salt a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, Ethylenediamino tetraacetic acid and up to -.100%, preferably 5 to 75 ß from at least a compound from the class of the alkali metal silicates, alkali metal carbonates and alkali metal borates.

The other auxiliaries and additives include the optical ones Brighteners in particular the foam inhibitors that are in the agents according to the invention present in an amount of up to 5%, preferably in an amount of 0.2 to -3% can be, furthermore, the enzymes in an amount up to 5/3, preferably 0.2 to 3 ß can be present and the carboxymothyl cellulose, the proportion of which is up to 5 %, preferably 0.2 to 3, can be.

Examples The graying-inhibiting effect of the following The compounds described in the examples were prepared by the known "soil redeposition" method checked [cf. H. STAPEL "Textil-Praxisl 'Bd. 3, page 264 (1954) 3 ion a laboratory washing machine (Launder-Ometer, ATLAS, Chicago USA) 4 lobes each from the tissue to be examined with a total weight of 8.3 g together with 1.3 g of one Artificially soiled cotton thread washed for 30 minutes up to three times.

Then the reflection value is measured with a photometer (Elrepho from the company CARL ZEISS, using filter no. 6).

The practical dust / sebum combination used to soil the cotton yarn consists of a mixture of kaolin, black iron oxide, soot and synthetic skin oil (from 1/3 traces of fat, 1/3 fat and 1/3 hydrocarbons). The cotton thread contains after soiling approx. 11 X pigments and approx. 2% sebum.

A detergent of the composition (in percent by weight) was used: 8 S n-dodecylbenzenesulfonate (Na salt) 3% oleyl alcohol with 10 ethylene glycol ether groups 3% Na soap from saturated Ci2-C22 fatty acids 40% pentasodium triphosphate 22 % Sodium perborate 3.5% sodium silicate (Na20: SiO2 = 1: 3.3) 2.5% magnesium silicate 0.2% Na nitrilotriacetate 0.3% optical brighteners.

4% of graying inhibitors were added to this agent.

The difference up to 100% was due to sodium sulfate.

The application concentration of the detergents was 5 g / l, the hardness of water 10 0du. The textile samples made from synthetic fabric as well as the mixed fabrics Refined cotton and synthetic fiber were refined at 40 to 600C, those made from Washed cotton at 95 ° C. The weight ratio of textile goods to washing liquor (Liquor ratio) was 1:30 or 1:12. After a washing time of 30 minutes the textile samples were rinsed four times with distilled water. After three washes the whiteness of the samples was determined photometrically. For comparison were Washing tests carried out without the use of a graying inhibitor. The results are compiled in the following table.

From the reflectance values it can be seen that when using the Polymers in all experiments one.

less graying of the textile fibers occurs. Was used instead of the Carboxymethylcellulose agents according to the invention were used for the tissues from synthetic fibers or those made from finished cotton, no significant improvement achieved compared to the comparison value without graying inhibitor, i.e. the increase the remission values were below 1%.

In the table, the abbreviations T mean the washing temperature and F the liquor ratio. The information "lxtl or 13x11" denotes the number of attempts. Cotton cotton polyester blended fabric ref. highly refined cotton / polyester Example polymer T = 95 ° CT = 60 ° CT = 60 ° CT = 60 ° C F = 1:12 F = 1:12 F = 1:30 F = 1:30 1x 3x 1x 3x 1x 3x 1x 3x 1. Sulphonated phenolic Formaldehyde resin 1.8: 1 mole ratio 74.2 70.2 71.7 70.4 61.1 53.2 68.2 52.8 Degree of sulfonation 1: 1 MG = 700 2. Sulphonated ß-naphthol Phenol-formaldehyde resin 1: 1: 1 molar ratio 74.4 70.6 71.7 70.3 61.5 53.2 67.6 55.3 Degree of sulfonation 1: 1 MG = 1200 3. sulfonated phenolic Formaldehyde resin, 2: 1 molar ratio 73.5 69.5 69.3 68.1 60.1 49.4 67.4 51.5 Degree of sulfonation 1: 1 MG = 1200 - without addition 71.3 63.3 67.4 65.0 57.1 45.7 66.8 49.0

Claims (3)

Claims 1. Detergent containing at least one Surface-active washing active substance and at least one building salt from the class the polymer phosphhates, sequestering agents and washing alkalis as well as at least containing a water-soluble alkali metal or ammonium salt of sulfonic acid groups Polycondensates, characterized in that the amounts of 0.1 to 10 wt present and a molecular weight of 500 to 1500 having salts of the polycondensates from a reaction product of one mole of formaldehyde and 1.6 to 2 moles of a compound from the class of phenols, naphthols and 1 to 4 carbon atoms in the alkyl group derived alkylphenols and, based on 2 aromatic groups, Contain 1 to 2 sulfonic acid groups. 2. Means according to claim 1, characterized in that the polymers are in the form of the sodium salts. 3. Means according to claim 1 and 2, characterized in that it contain up to 5% by weight, preferably 0.2 to 3% by weight, of carboxymethyl cellulose.